In the presence of a catalytic amount of mesoporous aluminosilicate (Al-MCM-41), both allyltrimethylsilane and silyl enol ether reacted with various acetals under mild reaction conditions to afford the corresponding homoallyl ethers and β-alkoxy ketones, respectively. The catalyst was easily recovered from the reaction mixture and could be reused in the same reaction without a significant loss of catalytic activity. Moreover, Al-MCM-41 exhibited high chemoselectivity for acetal over aldehyde in the reactions.